Blown wrinkle varnish base



Patented Apr. 10, 1945' BLOWN wnmxm VARNISH BASE William A. walaie, Dayton, Ohio, asslgnor to New Wrinkle, Inc., Dayton, Ohio, a corporation of Delaware No Drawing. Application December 22, 1941,

Serial N0. 424,010

a 5 Claims. (cl. zoo- 22) This invention relates to wrinkle varnish base and is a. continuation-in-part of my copendlng application Serial No. 335,615, filed May 16, 1940.

The primary purpose of this invention is the preparation of a wrinkle varnish base Comprising the reaction product of drying oil, oil' soluble resin and air at elevated temperature.

Hitherto the preparation of wrinkle varnish base has been considered to require the use oi- China-wood oil, oits'cica oil and other similar drying oils containing conjugated double bonds.

or mixtures of them. These oils or mixtures were generally used either in their raw or natural state or subssquent'to preliminary treatment as by blowing, depending on the particular characteristics required in the finished wrinkle varnish bas and the nature oithe individual oil or mixture of oils being used.

More recently, as disclosed in copending application Serial No. 312,742, filed January 6, 1940, use has been made of blown dehydrated castor oil as a substitute for the costly drying oils previously used in the preparation of wrinkle varnish base. I have discovered that a. wrinkle varnish base canbe produced by chemically combining un-v blowndrying type oil with oil soluble resin and air at elevated temperature.

usual manner, and the resulting composition produces a. durable finish particularly characterized by its hardness and'toughness.

As typical examples of formulations and procedures according to my invention, but without thereby limiting myself to the specific details of procedure and proportions indicated, thefollowing illustrative examples ar given:

The resulting product exhibits excellent wrinkling tendency with the addition of a small amount of drier in the temperature of approximately 300 F., whereupon th solvents are added.

The maleic acid resin may be of the type commercially available and sold under trade names such as Amberol 801, Beckacite 1110, Beckacite 1111 and Beckacite 1114, but, of course, other alkyd resins made from combinations of rosin,

glycerine and polybasic acid or anhydride prove suitable.

Example II Amoerol 801 pounds 100 Varnish grade linseed oll.- "gallons..- 12

Mineralspir'lt an 5 Solvesso #2 e do 16 Nuodex cobalt 6%' do In preparing the wrinkle varnish base from the above components, the resin is first melted in four gallons of oil by heating to a temperature of approximately 540 F. The balance or the oil is then addd and the mixture heated to app mately 400F. Air is then blown through the mixture to produce vigorous agitation and the temperature maintainedwlthin a. range or from 375 to 400 F. until the desired viscosity is obtained. A. satisfactory viscosity or end-point may be considered to have been reached when a drop falls from a stirring rod with a. slight thread-like filament while hot. When this condition has been reached the mixture is withdrawn from the fire and the solvent and drier added thereto.

In this instance, the mineral spirit is that grade of petroleum product of either a parafllnlc or naphthenic origin which is commonly known in the trade as turpentine substitute, while Solvesso #2 is a hydrogenated naphtha having a volatility similar to that of x'ylol and'manufactuned by Standard Oil Company. Nuodex cobalt 6% is a cobalt naphthenate drier solution in 40 which the metallic cobalt amounts to about 6%.

he end-point for the blowing step may be determined as previously mentioned; however, it

In preparing the varnish base from the aforementioned components approidmately one-half of the oil and all of the resin are placed in a kettle and heated rapidly to approximately 580 .F. The balance Of the oil is then added and the whole thoroughly mixed and removed from the me. The mixture is allowed to cool to approximately 400 F. whereupon air is blown through it and the mixture kept at a temperature ranging between 375 and 400 F. The air blowing is continued for approximately one hour, and the blown mixture. is then allowed to cool down to a may also be detennined by other means, as, for instance, by withdrawing test samples from time to time during the blowing operation, adding a predetermined amount of thinner to a definite weight of sample and comparing the viscosity of the resulting solution with viscosity standards.

, Example 111 v Amberol F-7 pounds i,

the Gardner-Holdt In preparing a wrinkle varnish base from the above components, the resin is melted in 8 sallons of the oil by heating to approximately 580 F. The mixture is then removed from the fire and-the balance of the oil added to it and the whole then heated to approximately 400 F. The temperature is held between 375 and 400 1''. and air blown through the mixture until the proper viscosity has been attained. The blown mixture is then removed from the fire and the mineral spirit added thereto. The thinned mixture is further diluted by adding the toluol as soon as the temperature has dropped to at least 300 F., at which time the cobalt drier is also added.

It will be noted that Amberol F-7 used in Example III is a rosin modified phenol-formaldehyde type of resin and, therefore, those skilled in the art will understand that other oil soluble and non-reactive phenol-aldehyde resins of the same general characteristics may be used in the practice of my invention. These include resins known by trade names such as Beckacite, Durez, Para-dura, Durite, Locto, Paranol, Varcum, etc. In every case an oil soluble and non-reactive quality must be employed.

The fundamental difference between the meth-- d of my invention and the product resulting from the practice thereof and the methods and products of the. prior art resides in the fact that wrinkle 'vamish bases hitherto produced are characterized by the fact .that they ld softer films at the same oil lengths than the wrinkle varnish base of my invention. Furthermore, the blown oils commonly used in the prior art exhibit auto-oxidizing tendencies due to the fact that they contain intermolecularly dispersed air which results in gradual and continuous oxidation and ultimately leads to separation of part of the oil as an insoluble gel thus rendering the product valueless for use in a varnish and particularly so when the varnish is part of a sprayable composition.

the oil', thetemperature of treatment being suf-- ficiently highto expel any non-combined air,

afsvaara check the bodyins thereof in the event that it hould have been blown a trifle too 1011:.

Likewise, many difierent driers may be used but preference should be given to those commonly known as top driers" and which tend to form thesurface skin which is so desirable in wrinkle compositions. The resinate, linoleate or naphthenate type of drier, characterized by ready soluthereby preventing the intermolecular dispersion which appears to be present in the case of blown According to my invention, oil, as such, ishot used in the preparation of the final wrinkle composition for it will be remembered that the oil and synthetic resin are coniointly aerated. In

bili y, proves very suitable for this purpose.

It will be understood that instead of the dehydrated castor oil and varnish grade linseed oil used in the examples tung oil, perilla oil, oiticica oil, soya bean oil, fish oil and other like oils having conjugated double bonds or mixtures thereof may be used, the choice depending primarily on the availability and cost. Those skilled in the art will understand that the Castung 2-3 used in Example 111 is a commercial grade of dehydrated castor oil.

The choice of resin will depend on the desired characteristics of the wrinkle varnish base. As has been noted hereinbefore, rosin modified alkyd resin-such a maleic acid resin may be used satisfactorily and it will be understood that other polybasic acids or their anhydrides, including phthalic, tartaric, citric and malic may be substituted for the maleic acid or anhydride, although the rosin modified maleic acid resin is preferred from among the almd resins. Likewise, other phenolaldehyde resins may be used in place of the Amberol and Durez resins hitherto mentioned.

Furthermore, natural resins such as Congo, kauri, Batu, Zanzibar, oil soluble Manila, Pontianak, etc., may be employed but where such naturalresins are used-they should first be "run" to make them oil soluble and the first step of the process hereinbefore described would have to be altered accordingly. In such case, the resin would first be fused, the first portion of the oil added to it, and the temperature raised to a point sufllcient to dissolve the resin in the oil, after which the second portion of the oil would be added and'the whole then submitted to the blowing step. The necessity for pretreating the natural resin will be fully appreciated by those skilled in the art.

The products resulting from the practice of Examples 2 and 3 are adapted for use as clear wrinkle finishes without further treatment; however, the product of Example I does not include the required metallic drier and has a consistency greater than permissible for proper spraying. A suitable wrinkle coating composition could be prepared from the product of Example I as follows:

Another type of drier suitable for use in E:- ample IV may be prepared as follows:

Example VI Cobalt linoleate solid. pounds 124s China-wood oil fatty acids.. do.. 8-10 Toluol, xylol, petroleum naphtha, etc.

4 gallons- 6- I It will be understood that metal driers other than cobalt compounds ma be used, such as those oimanganese. The inherent characteristicz-of the drier to be used is its ability to bring abouta rapid formation of a skin on the exposed surface of the film in order to causethe changes the'interior thereof which lead to the production of a wrinkle surface.

in volume between the surface of the, film and The wrinkle coating compositions of Examples 11, 111 and IV may be further compounded with pigment ground in oil vehicle for the purpose of and then baked at temperatures of from 200 to 250 F. for approximately one hour to produce a wrinkle finish characterized by its toughness and hardness.

It will be understood that while I have set forth certain specific embodiments of my inventlon, it isvnot my intention to have my invention limited to or circumscribed by the specific details of procedureand proportions indicated in view of the fact that my invention is adapted to changes according to individual preference and conditions without departing from the scope thereof as defined in the appended claims.

I claim:

1. The method of making wrinkle varnish base from .rosin modified alkyd resin and unblown drying oil which consists in heat reacting the resin with approximately one-half of the oil to be incorporated at approximately 580 F., adding cooling down to approximately 400 F., then vlg-- the other part of the oil to the mass and cooling down to approximately 400 F., then vigorously blowing air into the mixture for approximately one hour while a temperature of from 375 to 400 F. is maintained. a

2. The method of making wrinkle varnish base from rosin modified alkyd resin and unblown linseed oil whichconsists in heat reacting the resin with approximately one-half of the oil to be lncorporated at approximately 580 F., adding the other part of the oil to-the mass and cooling down to approximately 400 F., then vigorously blowing air into the'mixture for approximately one hour while'a temperature of from 375 to 400 F. is maintained.

3. The method of making wrinkle varnish base from rosin modified maleic acid alkyd resin and unblown drying oil which consists in heat reacting the resin with approximatelyone-half or the orously blowing air into 'the mixture for approximately one hour while a temperature of from 375 to 400 F. is maintained.

5. The method of making wrinkle coating composition from rosin modified alkyd resin and unblown drying oil which consists in heat reacting the resin with approximately one-half of the oil to be incorporated at approximately 580 E, adding the other part of, the oil to the mass andcooling down to approximately 400 1 then vigorously blowing air into the mixture for approximately one hour while a temperature of from 375 -to 400. F. is maintained, cooling the airblown reaction product down to approximately 300 F. and adding metallic drier and solvent.

6. The method of making wrinkle varnish base from rosin modified alkyd resin and unblown linseed oil which consists in heat reacting the.

resin with approximately one-half of the oil to be incorporated at approximately 580 F., adding'the other part of the oil to the mass and cooling down to approximately 400 F., then vigorously blowing air into the mixture for approximately one hour while a temperatureof from 375 to 400 F. is maintained, cooling the airblown reaction product down to approximately 300 F. and adding metallic drier and solvent.

7. The method of making wrinkle varnish base from rosin modified maleic acid alkyd resin and unblown drying oil which consists in heat, reacting the resin with approximately one-half of the oiLto' be incorporated at approximately 580 F., adding the other part of the oil to the mass and orously blowing air into the mixture for approximately one hour while a temperature of from 375 to 400 F. is maintained, cooling the airblown reaction product down to approximately 300 F. and adding metallic drier and solvent.

, 8. The method of making wrinkle-varnish base from rosin modified H aleic acid alkyd resin and unblown linseed oil w ch consists in heat reacting the resin with approximately one-half of the oil-t0 be incorporated at approximately 580 F., adding the other part of the oil to the mass and cooling down to approximately 400 F., then vigorously blowing air into the mixture for approximately one'hour while a temperature of from 3'75 to 400 F. is maintained, cooling the airblown reaction product down to approximately 300 F. and adding metallic drier and solvent.

oil to be incorporated at approximately 580 F.,

adding the other part of the oil to the mass and cooling down to approximately 400 F., then vigorously blowing air into the mixture for approximately one hour while a temperature of from 375 to 400 F. is maintained.

4. The method of making wrinkle varnish base from rosin modified maleic acid alkyd resin and unblown linseed oil which consists in heat reacting the resin with approximately one-half of the oil' to be incorporated at approximately 580 F., adding the other part of the oil to the mass and cooling down to approximately 400 R,- then vig- 9'. The air-blown heat reaction product of rosin modified alkyd resin and unblown drying oil obtained by heat reacting the resin with approximately one-half of the oil to be incorporated at approximately 580 F., adding the other part of the oil to the mass and cooling down to approximately 400 F., then vigorously blowing air into the mixture for approximately one hour while a temperature ofirom 375 to 400 F. is maintained.

10. The air-blown heat reaction product of rosin modified alkyd resin and unblown linseed oil obtained by heat reacting the resin with approximately one-half of the oil to be incorporated at approximately 580 F., adding the other part of the oil to themass and cooling down to approximately 400 F., then vigorously blowing air into the mixture for approximately one hour while a temperature of from 3'75 to 400 F. is maintained.

11. The air-blown heat reaction product of rosin modified maleic acid alkyd resin and unblown drying oil obtained by heat reacting the resin with approximately one-half of the oil to be incorporated at approximately 580 F., adding the other part oi the oil to the mass and cooling down to approximately 400 F., then vigorously blowing air into the mixture for approximately one hour while a temperature of from 375 to 400 7 1". is maintained.

12'. The air-blown heat reaction product of rosin modified maleic acid alkyd resin and unblown linseed oil obtained by heat reacting the resin with approximately one-half of the oil to be incorporated at approximately 580 F., adding the'other part of the oil to the mass and cooling down to approximately 400 F., then vigorously blowing air into the mixture for approximately one hour while a temperature of from 375 to 400 F. is maintained.

13. A wrinkle coating composition consisting of the air-blown heat reaction product of rosin- 14. A wrinkle coating composition consisting of l the air-blown heat reaction product of rosin modified alkyd resin, unblown linseed oil, metallic drier and solvent, obtained by heat reacting the resin with approximately one-half of the oil to be incorporated at approximately 580 F., adding the other part of the oil to the mass and ae'raam cooling down to approximately 400 i"., then vi:- orously blowing air into the mixture for approximately one hour while a temperature of from 375 to 400 F; is maintained, cooling the airblown reaction product down to approximately 300 F. and adding metallic drier and solvent.

15. A wrinkle coating composition consisting of the air-blown heat reaction product of rosin modified malelc acid alkyd resin, unblown drying oil, metallic drier and solvent, obtained by heat reactingthe resin with approximately one-half of the oil to be incorporated at approximately 580 F., addin the other part of the oil to the mass and cooling down to approximately 400 F., then vigorously blowing air into .the mixture for approximately one hour while a temperature of from 3'15 to 400 F. is maintained, cooling the air-blown reaction product down to approximately 300 F. and adding metallic drier and solvent.

16. A wrinkle coating composition consisting of the air-blown heat reaction product of rosin modified maleic acid alkyd resin, unblown linseed oil, metallic drier and solvent, obtained by heat reacting the resin with approximately one-half of the oil to be incorporated at approximately 580 F., adding the other part or the oil to the mass and cooling down to approximately 400 F., then vigorously blowing air into the mixture tor approximately one hour while-a temperature oi from 375 to 400 F.'is maintained, cooling the air-blown reaction product down to approximately 300 F. and adding metallic drier and solvent.

WILLIAM A. WaLDIE. 

